Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/54—Preparation of carboxylic acid anhydrides
  • C07C51/567—Preparation of carboxylic acid anhydrides by reactions not involving carboxylic acid anhydride groups

Definitions

• This invention relates to a method for the preparation of oxy-diphthalic anhydrides.
• the products are useful chemical intermediates for the further preparation of various compounds such as the corresponding dicarboxylic acids and the various derivatives thereof, including for example, the salts, esters, acyl halides, amides, imides and the like.
• the oxy-diphthalic anhydrides are particularly useful as monomers in the preparation of polyimides, for example by polycondensation with a suitable diamine, such as ethylenediamine or phenylenediamine.
• Japanese Patent Document No. 80/136, 246 (Chem. Abst. 95:42680) teaches the coupling of 4-nitrophthalic anhydride in the presence of sodium nitrite or potassium nitrate to form oxy-diphthalic oxy-diphthalic anhydride.
• Japanese Patent Document No. 80/122, 738 (Chem. Abst. 94:83799) discloses the reaction of 4-halophthalic acid or anhydride with an alkali metal hydroxide to yield oxy-diphthalic anhydride.
• Japanese Patent Document No. 80/27, 343 (Chem. Abstr. 94:191942) the reaction of 4-halo-phthalic anhydride, Na 2 CO 3 and NaNO 2 in dimethyl sulfoxide to form 4,4'-dihydroxydi- phthalylic anhydride is described.
• German Patent No. 2,416,594 (1975) discloses the coupling of 3-nitrophthalic anhydride in the presence of metal nitrites, such as sodium nitrite to form oxy-diphthalic anhydride.
• diphthalic ether dianhydrides of the formula ##STR1## can be prepared by reacting a halo-phthalic anhydride of the formula ##STR2## where Hal is F, Cl, Br or I, with an hydroxyphthalic anhydride of the formula ##STR3## in the presence of a polar, aprotic solvent and an alkali metal compound selected from the group consisting of KF, CsF and K 2 CO 3 .
• the ether bridge is formed at the site of the halo- and hydroxy-substituents on the phthalic anhydride reactants.
• the substituents of both reactants are at the 4-position, i.e., 4-halophthalic anhydride and 4-hydroxyphthalic anhydride
• the oxy-diphthalic product will be 4,4'-oxy-diphthalic anhydride, characterized by the formula ##STR4##
• the oxy-diphthalic product will be 3,3'-oxy-diphthalic anhydride characterized by the formula ##STR5##
• a mixture of 3-substituted and 4-substituted phthalic anhydrides such as 3-halophthalic anhydride and 4-hydroxyphthalic anhydride or 4-halophthalic anhydride and 3-hydroxyphthalic anhydride may be employed to prepare a 3,4-oxy-diphthalic anhydride of the formula ##STR6##
• the halogen substituent on the starting halophthalic anhydride reactant may be F, Cl, Br or I.
• the preferred reactant is fluorophthalic anhydride. It has been found that yield of oxy-diphthalic anhydride is surprisingly higher when fluorophthalic anhydride is employed than when other halophthalic anhydrides are employed as reactants under similar reaction conditions.
• the alkali metal compound may be potassium fluoride, cesium fluoride or potassium carbonate.
• the proportions of reactants may vary considerably, however, it is recommended that the alkali metal compound be employed in sufficient proportions to provide at least about one equivalent of potassium (or cesium) per mole of halo-phthalic anhydride.
• chloro-phthalic anhydride or bromo-phthalic anhydride reactants are employed together with potassium fluoride or cesium fluoride, it has been found efficacious to provide at least about two equivalents of alkali metal per mole of chloro- or bromo-phthalic anhydride.
• the alkali metal compound is employed in substantial excess, for example, up to about 50 percent excess, of the aforesaid equivalent proportions.
• the reaction be carried out under anhydrous conditions, to minimize the occurrence of undesired side reactions.
• the process of the invention is preferably carried out at atmospheric pressure, but super-atmospheric pressure, for example, under autogeneous conditions, may be employed, if desired.
• the process is preferably carried out in the presence of a polar, aprotic solvent such as N-methyl-pyrrolidone, dimethyl formamide, dimethyl acetamide, triglyme, sulfolane, or the like.
• the temperature at which the process is carried out may vary considerably, but will generally be within the range of about 120° to about 220° Celsius. Higher or lower temperature may be employed but are less efficient.
• the choice of solvent may govern the temperature employed. For example, at atmospheric conditions the boiling point of the solvent becomes a limiting condition. Moreover, the decrease in efficiency of the reaction as the temperature is lowered, varies somewhat with the solvent.
• the preferred temperature when using sulfolane as the solvent, is in the range of about 170°-215° and, most preferably, about 180°-190° Celsius.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Furan Compounds (AREA)
• Indole Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (8)

Applications Claiming Priority (1)

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Cited By (11)

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Citations (2)

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• 1987
  • 1987-08-24 US US07/088,325 patent/US4837404A/en not_active Expired - Fee Related
• 1988
  • 1988-08-05 WO PCT/US1988/002589 patent/WO1989001935A1/en not_active Application Discontinuation
  • 1988-08-05 BR BR888807384A patent/BR8807384A/pt not_active Application Discontinuation
  • 1988-08-05 EP EP19880907995 patent/EP0377637A4/en not_active Withdrawn
  • 1988-08-05 JP JP63507402A patent/JPH03500771A/ja active Pending
  • 1988-08-08 IL IL87379A patent/IL87379A/xx unknown
  • 1988-08-17 CA CA000574965A patent/CA1267907A/en not_active Expired - Fee Related
  • 1988-08-23 ES ES8802609A patent/ES2008003A6/es not_active Expired

Patent Citations (2)

Non-Patent Citations (1)

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